Mannich base polymers

ABSTRACT

A process for producing an oil soluble interpolymer polymer of 1,2-alkylenediamine such as N-ethyl ethylenediamine, aldehyde-provider such as formaldehyde, and ortho-unsubstituted hydroxyaromatics such as 4-polyalkylene phenol is disclosed. The decyclized Mannich Base monomer units provide a higher viscosity material which is suitably substituted with a long chain hydrocarbyl para substituent such as polyisobutylene or ethylene/alpha-olefin polymer. Various ortho-substituted hydroxyaromatics such as o-cresol may be used to control the degree of polymerization. The polymers are useful as dispersants or other lubricant additives.

BACKGROUND OF THE INVENTION

This invention relates to polymers derived from amines and hydroxyaromatic compounds, especially those suitable as Mannich Basedispersants, including conventional Mannich Base dispersants combinedwith such polymers. In the past, only the monomeric Mannich Basecondensates have been available and these are limited to relatively lowmolecular weight/viscosity, except as adjusted by the size of thephenolic substituent, usually a polymer of 300-10,000 number averagemolecular weight (Mw). Journal of Polymer Science, Part A, 31, at pages1955-1966 (1993) discloses a Mannich reaction of amines, formaldehyde,and phenols. Oil soluble hydroxyaromatic polymers are not taught. It hasbeen found desirable to provide a polymeric Mannich Base additive whoseviscosity/Mn can be adjusted by varying (especially limiting) the degreeof polymerization rather than by changing the para substituent. Theinvention accomplishes this need and coincidentally, can also providepolymers with small or no para substituent which are useful asthickeners, viscosity agents, or antioxidants.

Various Mannich Base productions have suggested use of a broad range ofcomponents and conditions but none have been shown to produce thepolymeric condensation adducts of the invention.

SUMMARY OF THE INVENTION

The invention is a process of forming an oil soluble hydroxyaromaticpolymer comprising heating (i) a 1,2-alkylenediamine, a hydroxyaromaticcompound having two open ortho positions, and more than an equivalent ofaldehyde functional group from an aldehyde-providing compound, perequivalent of primary amine in the 1,2-alkylenediamine or (ii) theircyclized Mannich Base, and forming an oil soluble hydroxyaromaticpolymer.

The invention is also a lubricant or additive concentrate comprising asynthetic lubricant and a polymer of a 1,2-alkylenediamine, ahydroxyaromatic compound having two open ortho positions, and analdehyde-providing compound. The invention is also the above compositionwherein said polymer has structural units of: ##STR1## wherein each R isindependently selected H or hydrocarbyl.

The invention is also a lubricant or additive concentrate comprising anoil soluble ring-opened polymer of: ##STR2##

The invention is also a Mannich Base having the structure ##STR3##wherein the R's are independently selected H or hydrocarbonyl whereinthe R on the para position of the aromatic ring has five or more carbonatoms.

The process of the invention provides sufficient amounts of oil solubleMannich Base condensate polymers for use as lubricating oil additives.The polymers are characterized by the advantageous producibility ofadjustable viscosity properties to permit ready handling. The polymersare also especially useful in a novel composition of syntheticlubricating oil or a blend of conventional and synthetic oils.

Various polymers of the invention having a small or no substituent parato the hydroxyl group of the hydroxyaromatic compound, are also usableas additives for antioxidant or other additive or Mannich Base use. Metasubstituents are optional.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The process of the invention is suitable for providing sufficientportions of the condensation adduct polymers of the invention for use asdispersants and other additives.

According to the invention, polymers of Mannich Base condensationadducts are prepared from certain hydroxyaromatics,1,2-alkylenediamines, and aldehyde-providers/producers.

The hydroxyaromatics usable in the invention are a broad class ofaromatic compounds having at least one hydroxyl group or the equivalentand having two open ring positions adjacent to the hydroxyl(s), for apolymerization route. Thus the hydroxyaromatic compounds include thoseof structure ##STR4## wherein Ar is phenyl, naphthenyl, anthracenyl,etc., such that b is usually 1, 2, or 3, conveniently 1 (phenyl), and ais one or more. Included are 1-naphthol, 2-naphthol, etc.,hydroxyaromatics. These hydroxyaromatics have two open ortho positionsfor substitution in polymerization.

Suitable compounds include phenols, especially substituted phenols suchas para-nitrophenol, para-alkylphenols preferably wherein the alkylsubstituent is as or higher alkyl and other straight and branched chainalkyls and hydrocarbyls including (and preferably) polymers. Thepreferred polymer para substituents include polyalkenes such aspolyisobutylene and ethylene/alpha-olefin interpolymers. The latterinclude ethylene/propylene and ethylene/butene copolymers. Copolymers oftwo alpha-olefins such as butene/propylene copolymer or a homopolymersuch as atactic propylene, are also suitable ligands on thehydroxyaromatic compound. The meta positions are optionally substitutedbut such starting materials are not widely available. Such substitutedhydroxyaromatics are suitable so long as the polymerization process isnot prevented by their presence.

Other suitable hydroxyaromatics include the polyhydroxyl aromatics suchas catechol, resorcinol, hydroquinone, and the polynuclearpolyhydroxyls.

Also included are hydroxyl-equivalent aromatics such as bisphenols(diphenyl ethers). The above-mentioned substituents for phenols applyequally to the various polyhydroxyls and polynuclear aromatics.

The phenolic compounds are readily supplied by known routes. Phenols arealkylated with heating or using catalysts. Lower temperature alkylation,generally below 40° C. provides predominantly para-alkylated productswhereas higher temperatures provide more ortho-substituted phenols andortho-directing catalysts such as zeolites provide generally higher, upto about 60 percent ortho products. Solid acid catalysts often giveabout 50 percent ortho and 50 percent para-substituted products. For BF₃alkylation of polyisobutylene onto phenol, lower temperature isgenerally used to avoid polymer degradation. Ethylene/alpha-olefinpolymers are not so acid sensitive.

The non-ortho substituent of the hydroxyaromatic compound is preferablya polymeric substituent such as polyisobutylene or various otherhomopolymers including atactic polypropylene; or ethylene/alpha-olefin(EAO) interpolymers especially ethylene/propylene, ethylene/butene, andother copolymers. The EAO polymer substituents conveniently range from20-80 molar percent ethylene with Mn of about 300-10,000, such as700-5000 as commonly measured by GPC. The polymers are generallyamorphous and oil soluble. In a preferred embodiment, the polymersubstituent is derived from an EAO of at least about 30 percent terminal(preferably ethylidene) unsaturation. Such polymers are readily preparedfrom various metallocene catalyst systems as are well known in the art(typically with a methyl alumoxane cocatalyst).

The aldehyde-providing or aldehyde-producing entities of the inventioninclude formaldehyde and its equivalents in various forms. These includeparaformaldehyde, polyformaldehyde, aqueous formaldehyde, and trioxane.Other aldehyde group-containing compounds such as C₂ -C₁₀ hydrocarbylaldehydes (e.g., butyraldehyde, acetaldehyde, propionaldehyde, etc.) canalso be employed. Preferred are those of the formula RCHO wherein R is Hor C₁ -C₄ hydrocarbyl.

The aldehyde providing compounds supply an "aldehyde," ##STR5## i.e.,equivalents of aldehyde functional group for Mannich Base reaction andpolymerization.

The 1,2-alkylene diamines of the invention have a primary amine bydefinition. These diamines may be polyamines, may have varioussubstituents, especially hydrocarbyl including alkyl, and may bestraight or branched chain diamines. They generally have the structure##STR6## wherein the R's are hydrocarbyl, preferably alkyl, optionallywith other substituents especially amino groups.

Thus, the R attached to the nitrogen may be nitrogen-containinghydrocarbyls. In other words, the above structure may representpolyamines such as diethylene triamine, triethylene tetramine,tetraethylene pentamine, pentaethylene hexamine and otherpolyethyleneamines and polyalkylene amines as well as other polyamineslike N₃ (3 nitrogens) or higher polyamines optionally with variedsubstituents and groups linking nitrogen atoms.

In one embodiment of the invention, the R on the nitrogen may be apolymer substituent such as a PIB or EAO as described herein.

The 1,2-alkylene diamines include those of about 2 to 60, preferably 2to 20 carbon atoms and about 2 to 12, preferably 2 to 9 nitrogen atomsin the molecule. These diamines may be hydrocarbyl amines which includeother groups such as hydroxyls, alkoxys, amides, (?)nitriles,imidazolines, etc. Convenient amines include commercially availablepolyamines and any polyoxyalkylenes which are 1,2-alkylene diamines.

Non-limiting examples of suitable 1,2-alkylene diamines are polyethyleneamines such as diethylene triamine, triethylene tetramine,tetraethylene, pentamine, polypropylene amines such as 1,2-propylenediamine, di-(1,2-propylene) triamine, and N-aminoalkyl piperazineshaving a 1,2-alkylene diamine terminus. N-alkyl ethylene diamine,including N-ethyl ethylenediamine, are a convenient class. Commercialproducts and mixtures of amines may be used. These include those soldunder the trade names "Polyamine H", "Polyamine 400", and "Dow PolyamineE-100", as well as those heavy polyamines having an equivalent weight ofabout 120-160 grams per equivalent of primary amine and at least about28 wt. percent nitrogen; alternatively having at least about seven (7)nitrogens per molecule and an equivalent weight of about 125-140 gramsper equivalent of primary amine; alternatively having less than about 1wt. percent pentamines and lower polyamines and less than about 25 wt.percent hexamines, optionally with substantially no oxygen. Amido aminessuch as those disclosed in U.S. Pat. No. 4,857,217 may be used.

Various common hydrocarbyl solvents are usable in the invention insuitable proportions to readily carry out the reaction. These solventsinclude heptane, n-propanol, pentane, hexane, butanol, etc. The1,2-alkylene diamines and hydroxyaromatics undergo Mannich Basecondensation according to the invention by providing more than anequivalent of aldehyde-providing compound per equivalent of primaryamine in the 1,2-alkylene diamine. The additional portion of aldehyde(provider) permits and favors production of five-membered rings from1,2-alkylene diamines. For example, N-alkyl 1,2-ethylenediaminecondenses with two equivalents of formaldehyde and apara-hydrocarbylphenol to form: ##STR7## wherein R on the nitrogen isthe alkyl group from the diamine and the R on the phenolic ring is thehydrocarbyl group from the phenolic reactant.

According to the invention, upon heating such compounds, the ring opensbetween the nitrogens and polymerizes to form polymers having thestructural units ##STR8## wherein the R's are as described above.Similarly, other aldehydes (providers) and hydroxyaromatics and1,2-alkylenediamines form various polymers which may have othersubstituents. More equivalents of aldehyde functional groups arerequired for each additional primary amine in the 1,2-alkylenediamine toprovide ring formation and, ultimately, polymerization as indicated.Also, with additional aldehyde, additional ring formation may beprovided at two secondary amines separated by an ethylene or substitutedethylene linkage in polyamines. Such 5-membered rings in the polyaminemay be opened on heating to condense with a hydroxyaromatic compound.

It is noted that those hydroxyaromatics not having two open orthopositions, while condensing with the five-membered ring from aldehydeand 1,2-alkylenediamine do not polymerize on heating.

Thus, e.g., the five-membered ring condensates with ortho cresol do notform polymer. This may, however, be used to advantage by proceeding withmixtures of hydroxyaromatics which permit polymerization and,selectively, a chain stopper of conventional type or an ortho-blockedhydroxyaromatic. Concurrently then, e.g., a portion of ortho-t-butylphenol admixed with para-t-butyl phenol may be used to limit Mn andviscosity of the polymer.

Preferably about two (2) or more equivalents of aldehyde producer,preferably formaldehyde, are used per equivalent of primary amine topromote ring formation.

Heating is used either during the condensation, reaction to proceed topolymer in one step, or after condensation to open the 5-membered ringand form the polymer according to the invention.

Heating temperature to form the polymer of the invention variesaccording to the reactants used to form the condensate and therebyaffecting the stability of the 5-membered ring. Generally, the heatingtemperature for most common condensates is about 150° C. or higher,preferably 160° C. or higher.

The polymers of the invention have a broad spectrum of utility inoleaginous compositions. Most notably, the polymers of the invention,either alone or in combination with Mannich Base or other dispersants,serve as dispersants/compositions for admixture with lubricants andfuels. The novel combination of the polymers of the invention with asynthetic oil or synlube composition is especially advantageous becausesuch synthetic oil compositions require viscosity modification and suchviscosity alteration is obtainable by proper selection of dispersantused in the oil. Moreover, by means of this invention, the viscosityalteration may be achieved by altering either the hydrocarbyl (alkyl,polymeric, etc.) substituent in the para (or comparable) position of thehydroxyaromatic compound or by regulating either the amount of aldehydeor amount of para-substituted hydroxyaromatic chain terminator.

The polymers and polymer Mannich Base mixtures of the invention arereadily post treated such as by boration with boric acid boron oxide,boron halides, boron esters or other boron-attaching compounds, or bycapping with known materials such as dodecycl succinic anhydride, maleicanhydride, polyisobutenyl/succinic anhydrides of varied molecularweights and other acylating agents. Such treatments tend to assurebetter interaction with elastomer/rubber seals which come into contactwith the additives/dispersants/mixtures of the invention in oils.

The boration should be sufficient to provide from about 0.1 to 20 atomicproportions of boron for each mole of nitrogen composition. The borateddispersants of the invention usefully contain about 0.05 to 2.0 wt.percent boron. Treating is readily carried out by combining a slurry ofboric acid to an oil solution of the dispersant at 135°-190° C. for 1 to5 hours, followed by nitrogen stripping.

The polymers and mixtures of the invention can also be treated withpolymerizable lactones such as epsilon caprolactone to form adducts.Similarly, the polymers and mixtures of the invention may be complexedwith metal reactants such as metal nitrates, halides, phosphates,sulfates, borates, etc., of iron, cobalt, nickel, copper, chromium, etc.

The polymers, mixtures, and other additives of the invention arecombined with oils and fuels in conventional manner or any convenientway including use of elevated temperature.

The polymers and mixtures of the present invention possess very gooddispersant properties as measured herein in a wide variety ofenvironments. Accordingly, the dispersants/additives are used byincorporation and dissolution into an oleaginous material such as fuelsand lubricating oils. When the dispersants/additives of this inventionare used in normally liquid petroleum fuels such as middle distillatesboiling from about 65° to 430° C., including kerosene, diesel fuels,home heating fuel oil, jet fuels, etc., a concentration of the additivesin the fuel in the range of typically from about 0.001 to about 0.5, andpreferably 0.005 to about 0.15 weight percent, based on the total weightof the composition, will usually be employed.

The polymers and mixtures of the present invention find their primaryutility in lubricating oil compositions which employ a base oil in whichthe additives redissolved or dispersed. Such base oils may be natural orsynthetic. Base oils suitable for use in preparing the lubricating oilcompositions of the present invention include those conventionallyemployed as crankcase lubricating oils for spark-ignited andcompression-ignited internal combustion engines, such as automobile andtruck engines, marine and railroad diesel engines, and the like.Advantageous results are also achieved by employing the polymers andmixtures of the present invention in base oils conventionally employedin and/or adapted for use as power transmitting fluids, universaltractor fluids and hydraulic fluids, heavy duty hydraulic fluids, powersteering fluids and the like. Gear lubricants, industrial oils, pumpoils and other lubricating oil compositions can also benefit from theincorporation therein of the polymers and mixtures of the presentinvention.

These lubricating oil formulations conventionally contain severaldifferent types of additives that will supply the characteristics thatare required in the formulations. Among these types of additives areincluded viscosity index improvers, antioxidants, corrosion inhibitors,detergents, dispersants, pour point depressants, antiwear agents,friction modifiers, and other ashless dispersant (e.g., polyisobutenylsuccinimides) and borated derivatives thereof), etc.

In the preparation of lubricating oil formulations it is common practiceto introduce the additives in the form of 10 to 80 wt. %, e.g., 20 to 80wt. % active ingredient concentrates in hydrocarbon oil, e.g. minerallubricating oil, or other suitable solvent. Usually these concentratesmay be diluted with 3 to 100, e.g., 5 to 40 pads by weight oflubricating oil, per part by weight of the additive package, in formingfinished lubricants, e.g. crankcase motor oils. The purpose ofconcentrates, of course, is to make the handling of the variousmaterials less difficult and awkward as well as to facilitate solutionor dispersion in the final blend. Thus, a dispersant would be usuallyemployed in the form of a 40 to 50 wt. % concentrate, for example, in alubricating oil fraction.

The ashless dispersants of the present invention will be generally usedin admixture with a lube oil basestock, comprising an oil of lubricatingviscosity, including natural and synthetic lubricating oils and mixturesthereof.

Natural oils include animal oils and vegetable oils (e.g., castor, lardoil) liquid petroleum oils and hydrorefined, solvent-treated oracid-treated mineral lubricating oils of the paraffinic, naphthenic andmixed paraffinic-naphthenic types. Oils of lubricating viscosity derivedfrom coal or shale are also useful base oils.

Alkylene oxide polymers and interpolymers and derivatives thereof wherethe terminal hydroxyl groups have been modified by esterification,etherification, etc., constitute another class of known syntheticlubricating oils. These are exemplified by polyoxyalkylene polymersprepared by polymerization of ethylene oxide or propylene oxide, thealkyl and aryl ethers of these polyoxyalkylene polymers (e.g.,methyl-poly isopropylene glycol ether having an average molecular weightof 1000, diphenyl ether of poly-ethylene glycol having a molecularweight of 500-1000, diethyl ether of polypropylene glycol having amolecular weight of 1000-1500); and mono- and polycarboxylic estersthereof, for example, the acetic acid esters, mixed C₃ -C₈ fatty acidesters and C₁₃ oxo acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils comprises theesters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acids and alkenyl succinic acids, maleic acid, azelaic acid,suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic aciddimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with avariety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecylalcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycolmonoether, propylene glycol). Specific examples of these esters includedibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctylsebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate,didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester oflinoleic acid dimer, and the complex ester formed by reacting one moleof sebacic acid with two moles of tetraethylene glycol and two moles of2-ethylhexanoic acid.

Esters useful as synthetic oils also include those made from C₅ to C₁₂monocarboxylic acids and polyols and polyol ethers such as neopentylglycol, trimethylolpropane, pentaerythritol, dipentaerythritol andtripentaerythritol.

Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, orpolyaryloxysiloxane oils and silicate oils comprise another useful classof synthetic lubricants; they include tetraethyl silicate,tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate,tetra-(4-methyl-2-ethylhexyl)silicate,tetra-(p-tert-butylphenyl)silicate, hexa-(4-methyl-2-pentoxy)disiloxane,poly(methyl)siloxanes and poly(methylphenyl)siloxanes. Other syntheticlubricating oils include liquid esters of phosphorus-containing acids(e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester ofdecylphosphonic acid) and polymeric tetrahydrofurans.

Unrefined, refined and rerefined oils can be used in the lubricants ofthe present invention. Unrefined oils are those obtained directly from anatural or synthetic source without further purification treatment. Forexample, a shale oil obtained directly from retorting operations, apetroleum oil obtained directly from distillation or ester oil obtaineddirectly from an esterification process and used without furthertreatment would be an unrefined oil. Refined oils are similar to theunrefined oils except they have been further treated in one or morepurification steps to improve one or more properties. Many suchpurification techniques, such as distillation, solvent extraction, acidor base extraction, filtration and percolation are known to thoseskilled in the art. Rerefined oils are obtained by processes similar tothose used to obtain refined oils applied to refined oils which havebeen already used in service. Such rerefined oils are also known asreclaimed or reprocessed oils and often are additionally processed bytechniques for removal of spent additives and oil breakdown products.

Various other typical additive package components and individualadditives are also usable in the compositions of the invention. Theseinclude metal-containing rust inhibitors and/or detergents such as metalsalts of sulphonic acids, alkyl phenols, alkyl salicylates and otheroil-soluble acids and highly basic metal salts and magnesium/calciumsulphonates or phenates; viscosity modifiers such as Mn of 10⁴ -10⁶hydrocarbyl polymers/copolymers (ethylene/propylene) and polyestermodifiers such as methacrylic acid, etc., antiwear agents such asdihydrocarbyl dithiophosphate metal salts like zinc salts; conventionalor multifunctional antioxidants including copper salts; corrosioninhibitors such as phosphosulfuized hydrocarbon; oxidation inhibitorslike alkylphenol thioesters; friction modifiers; pour point depressants;rust inhibitors; demulsifiers; and other compatible additives.

Thus additives for lubes such as two and four cycle additives, toimprove engine cleanliness, can be prepared by Mannich base reaction ofpolymer alkylated phenols with more than 1 equivalent of aldehyde perequivalent of primary amino group in a polyethylene amine, andsubsequently heating of the Mannich base intermediate to produce apolymeric product. Another aspect of this invention is to control theviscosity growth of the polymerized Mannich base by using either amixture of ortho/para polymer alkylated phenol or using a mixture ofphenol and cresol to produce the polymer alkylated phenol.

The higher the percentage of ortho blocked product, the lower theviscosity growth of the additive.

EXAMPLES Example 1

The formation of a Mannich base according to the invention shown wasproduced by combining 4.06 g N-Ethyl ethylenediamine (2.4:1 ratio toprimary amine), 6.90 g para-t-butyl phenol 3.36 g paraformaldehyde and40 g heptane diluent, and heating for 3 hours at reflux (˜80° C.).Carbon 13 nuclear magnetic resonance spectroscopy ("¹³ C NMR"), afterremoval of volatiles on a rotary evaporator, gave the structure:##STR9## Attempted vacuum distillation of this liquid led to initialreflux in the still until the pot temperature reached about 160° C.whereupon the contents polymerized in an instant. Solid state ¹³ C NMRdisplayed a ring opened structure consistent with the invention.

Example 2

Example 1 was repeated. After removal of solvent by means of a rotaryevaporator, an attempt was made to distill the liquid product at highvacuum by means of a short path Kugelrohr apparatus.

Heating to 160° C. gave a small amount of solid in the collection bulb.

Analysis: C, 73.71; H, 9.48; N 9.22, O 8.30

The majority of the product polymerized in the distillation bulb.

Analysis: C, 75.10; H, 9.23; N, 7.03; 0.855.

Comparative Example 3

An ortho substituted phenol 2-tert-butyl-4-methyl phenol was substitutedfor the 4-t-butyl phenol of example 2.

A liquid Mannich base adduct was produced and showed a ¹³ C NMRconsistent with the structure: ##STR10## Short path distillation atabout 140° C. at 0.05 mm showed that this product was distillable.Heating at 160° C. produced no polymer. Similar results are achievedwith ortho-t-butyl phenol.

Thus, an ortho substituent blocks polymerization.

Example 4

Triethylene tetramine (TETA) 5.11 g; paracresol, 7.56 g;paraformaldehyde 5.18 g; Decane 1.52 g; and n-propanol 60.82 g wereplaced in a Parr pressure reactor and heated to 160° C. with stirring.Solid polymer was recovered.

Analysis: C, 69.05, 69.34; H 8.14, 8.15, O, 8.35,8.51; N, 12.29, 12.35.

Solid state ¹³ C NMR showed an opened ring polymer structure similar toexample 1.

A series of experiments with phenol alkylated with copolymers ofethylene and butene-1, showed that the use of about 2 moles offormaldehyde per primary amine of commercial polyamine (PAM) "Dow E-100"gave Mannich base products which could show large increases in viscosityupon heating at elevated (>150° C.) temperatures. Interestingly,ortho/para alkylated phenol adducts showed significant viscosity growthupon heating but not nearly as severe as the viscosity increase fromessentially all para alkylated phenol as shown below.

Example 5

This example illustrates the Mannich Base dispersant using 1.2 moles offormaldehyde per mole of primary amine when the intermediate is heatedto 160° C. for 1 hour and the polymer alkylate comprises 30% ortho and70% para. About 3148 grams (0.874 mol) of an ethylene/butene phenolalkylate (Mn=3600) was charged into a reactor and mixed with 99.6 gramsof polyethylene amine (PAM) having 8.82 meq of primary amine per gram ofPAM. The reactor mixture was heated to 90° C. and stirred under nitrogenatmosphere while adding 85.5 grams of formalin (37 percent aqueoussolution of formaldehyde) over 25 minutes and then soaked at 90° C. fortwo hours. The reactor temperature was then increased to 165° C. andkept at this temperature for one hour and 2018 grams of mineral oilS150N were added. The viscosity of the Mannich Base intermediate was 717cst at 100° C. The cool down product was kept at 140° C. and 289.4 gramsof a 30% boric acid slurry was added over 15 minutes. The reactortemperature was increased to 160° C. and soaked for two hours. Then 1386grams of mineral oil S100 neutral were added and the product wasfiltered. The 40% active ingredient solution analyzed for: 0.48%nitrogen with a viscosity of 3370 cst at 100° C.

Example 6

This example illustrates the Mannich Base dispersant using 2.0 moles offormaldehyde per mole of primary amine when the intermediate is heatedto 160° C. for one hour and the polymer alkylate comprises 30% ortho and70% para. About 3165 grams (0.88 mol) of an ethylene/butene phenolalkylate (Mn=3600) was charged into a reactor and mixed with 100.2 gramsof polyethylene amine (PAM) having 8.82 meq of primary amine per gram ofPAM. The reactor mixture was heated to 90° C. and stirred under nitrogenatmosphere while adding 143 grams of formalin (37 percent aqueous) over25 minutes and then soaked at 90° C. for two hours. The reactortemperature was then increased to 165° C. and kept at this temperaturefor one hour and 2037 grams of mineral oil S150N were added. Theviscosity of the Mannich Base intermediate was 783 cst at 100° C. Thecool down product was kept at 140° C. and 291 grams of a 30% boric acidslurry was added over 15 minutes. The reactor temperature was increasedto 160° C. and soaked for two hours. Then 2,395 grams of mineral oilS100 neutral were added and the product was filtered. The 35% activeingredient solution analyzed for: 0.40% nitrogen with a viscosity of16,250 cst at 100° C.

Example 7

This example illustrates the Mannich Base dispersant using 1.2 moles offormaldehyde per mole of primary amine when the intermediate is heatedto 160° C. for 4 hours and the polymer alkylate comprises 44% ortho and56% para. About 3394 grams (1.04 mol) of an ethylene/butene phenolalkylate (Mn=3250) was charged into a reactor and mixed with 136.6 gramsof polyethylene amine (PAM) having 8.82 meq of primary amine per gram ofPAM. The reactor mixture was heated to 90° C. and stirred under nitrogenatmosphere while adding 117.2 grams of formalin over 25 minutes and thensoaked at 90° C. for two hours. The reactor temperature was thenincreased to 165° C. and kept at this temperature for four hours and2,169 grams of mineral oil S150N were added. The cool down product waskept at 140° C. and 396.7 grams of a 30% boric acid slurry was addedover 15 minutes. The reactor temperature was increased to 160° C. andsoaked for two hours. Then 1,519 grams of mineral oil S100 neutral wereadded and the product was filtered. The 40% active ingredient solutionanalyzed for: 0.57% nitrogen with a viscosity of 2420 cst at 100° C.

Example 8

This example illustrates the Mannich Base dispersant using 2.0 moles offormaldehyde per mole of primary amine when the intermediate is heatedto 160° C. for 4 hours and the polymer alkylate comprises 44% ortho and56% para. About 3199 grams (0.98 mol) of an ethylene/butene phenolalkylate (Mn=3250) was charged into a reactor and mixed with 127.8 gramsof polyethylene amine (PAM) having 8.82 meq of primary amine per gram ofPAM. The reactor mixture was heated to 90° C. and stirred under nitrogenatmosphere while adding 182.4 grams of formalin over 25 minutes and thensoaked at 90° C. for two hours. The reactor temperature was thenincreased to 165° C. and kept at this temperature for four hours and2,053 grams of mineral oil S150N were added. The cool down product waskept at 140° C. and 371.2 grams of a 30% boric acid slurry was addedover 15 minutes. The reactor temperature was increased to 160° C. andsoaked for two hours. Then 1,026 grams of mineral oil S 100 neutral wereadded and the product was filtered. The 40% active ingredient solutionanalyzed for: 0.52% nitrogen with a viscosity of 3370 cst at 100° C.

Example 9

This example illustrates the Mannich Base dispersant using 1.08 moles offormaldehyde per mole of primary amine when the intermediate is heatedto 140° C. for 2 hours and the polymer alkylate comprises 54% ortho and46% para. About 4.100 grams (0.0414 mol) of an ethylene/butene phenolalkylate (Mn=2016) was charged into a reactor and mixed with 4.8 gramsof polyethylene amine (PAM) having 8.82 meq of primary amine per gram ofPAM. The reactor mixture was heated to 90° C. and stirred under nitrogenatmosphere while adding 3.7 grams of formalin over 5 minutes and thensoaked at 90° C. for two hours. The reactor temperature was thenincreased to 140° C. and kept at this temperature for four hours and 158grams of mineral oil S150N were added. Then 2.73 grams of boric acid wasadded over 15 minutes. The reactor temperature was increased to 160° C.and soaked for two hours. The nitrogen stripped product was filtered.The product analyzed for 0.5 6% nitrogen with a viscosity of 166 cst at100° C.

Example 10

This example illustrates the Mannich Base dispersant using 2.16 moles offormaldehyde per mole of primary amine when the intermediate is heatedto 140° C. for 2 hours and the polymer alkylate comprises 54% ortho and46% para. About 100 grams (0.0414 mol) of an ethylene/butene phenolalkylate (Mn=2016) was charged into a reactor and mixed with 4.8 gramsof polyethylene amine (PAM) having 8.82 meq of primary amine per gram ofPAM. The reactor mixture was heated to 90° C. and stirred under nitrogenatmosphere while adding 7.4 grams of formalin over 5 minutes and thensoaked at 90° C. for two hours. The reactor temperature was thenincreased to 140° C. and kept at this temperature for four hours and 158grams of mineral oil S150N were added. Then 2.73 grams of boric acid wasadded over 15 minutes, The reactor temperature was increased to 160° C.and soaked for two hours. The nitrogen stripped product was filtered.The product analyzed for: 0.5 6% nitrogen with a viscosity of 302 cst at100° C.

Example 11

This example illustrates the Mannich Base dispersant using 1.1 moles offormaldehyde per mole of primary amine when the intermediate is heatedto 145° C. for 2 hours and the polymer-phenol is primarily alkylated atthe para position (91% para, 9% ortho). About 50 grams (0.022 mol) of anethylene/butene phenol alkylate (Mn=2300) was charged into a reactor andmixed with 2.5 grams (0.022 eq. primary amine) of polyethylene amine(PAM) having 8.68 meq of primary amine per gram of PAM. The reactormixture was heated to 90° C. and stirred under nitrogen atmosphere whileadding 0.74 grams (0.0240 mol) of paraformaldehyde over half hour andthen soaked at 90° C. for two hours. The reactor temperature was thenincreased to 145° C. and kept at this temperature for four hours and 57grams of mineral oil S150N were added. Then 4.27 grams of a 30% boricacid oil slurry was added over 15 minutes. The reactor temperature wasincreased to 150° C. and soaked for two hours. The nitrogen strippedproduct was filtered. The product was analyzed for: 0.5 4% nitrogen witha viscosity of 230 cst at 100° C.

Example 12

This example illustrates the Mannich Base dispersant using 3.0 moles offormaldehyde per mole of primary amine when the intermediate is heatedto 145° C. for 2 hours and the polymer-phenol is primarily alkylated atthe para position (91% para, 9% ortho). About 50 grams (0.022 mol) of anethylene butene phenol alkylate (Mn=2300) was charged into a reactor andmixed with 2.5 grams (0.022 eq. primary amine) of polyethylene amine(PAM) having 8.68 meq of primary amine per gram of PAM. The reactormixture was heated to 90° C. and stirred under nitrogen atmosphere whileadding 2.0 grams (0.066 mol) of paraformaldehyde over half hour and thensoaked at 90° C. for two hours. The reactor temperature was thenincreased to 145° C. and kept at this temperature for four hours and 57grams of mineral oil S150N were added. Then 4.27 grams of a 30% boricacid oil slurry was added over 15 minutes. The reactor temperature wasincreased to 150° C. and soaked for two hours. The product became veryviscous while heating. It analyzed for 0.59% N. The viscosity could notbe measured because the product in oil solution was too thick to measureat the bath temperature.

Example 13

The polymer of Example 11 replaces the conventional dispersant of anadditive package in a passenger car motor oil formulation usingpolyalpha-olefin synthetic lubricating oil.

A reduced amount of viscosity modifier is necessary to provideappropriate viscosity at low and high engine temperatures.

Example 14

A synthetic lubricant is prepared as in Example 13 except that more than95 wt. percent of the dispersant portion is a conventional Mannich Basedispersant and less than 5 wt. percent is the polymer of Example 11 toflexibly provide a slight increase in viscosity.

We claim:
 1. A process of forming an oil soluble hydroxyaromatic polymercomprising heating (i) a 1,2-alkylenediamine; a hydroxyaromatic compoundhaving two open ortho positions; and more than an equivalent of aldehydefunctional group from an aldehyde-providing compound, per equivalent ofprimary amine in the 1,2-alkylenediamine or (ii) their cyclized MannichBase; and forming an oil soluble hydroxyaromatic polymer.
 2. The processof claim 1, wherein the heating is carried out at about 160° C. orhigher.
 3. The process of claim 1 with about 2 or more equivalents ofaldehyde functional group per equivalent of primary amine.
 4. Theprocess of claim 1 wherein said aldehyde-providing compound is aformaldehyde.
 5. The process of claim 1 wherein said 1,2-alkylenediamine is an N₃ or higher polyamine or polyethylene amine.
 6. Theprocess of claim 1 wherein polymerization is limited by the presence ofan ortho substituted hydroxyaromatic.
 7. An oil soluble polymer preparedby the process of claim 1, comprising a ring-opened polymer of acyclized Mannich Base condensation adduct of a 1,2-alkylenediamine and ahydroxyaromatic compound.
 8. An oil soluble polymer of claim 7, havingstructural units of: ##STR11## wherein each R is independently selectedfrom the group consisting of H and hydrocarbyl.
 9. A polymer of claim 7,wherein said hydroxyaromatic compound is a phenol having a parapolymeric substituent.
 10. A composition of a Mannich Base and at leastabout 5 wt. percent of a copolymer of claim
 7. 11. A Mannich Base havingthe structure ##STR12## wherein the R's are independently selected fromthe group consisting of H and hydrocarbyl wherein the R on the paraposition of the aromatic ring has five or more carbon atoms.
 12. TheMannich Base of claim 11 wherein the R on the para position of thearomatic ring is a polymer.
 13. The ring-opened polymer of the MannichBase of claim
 11. 14. The polymer of claim 13 wherein the R on thenitrogen is a nitrogen containing hydrocarbyl group.
 15. The MannichBase of claim 11 derived from an N₃ or higher polyamine.